Graft copolymers of mixtures of acrylamides and sulfonic acid compounds on n-vinyl-3-morpholinone polymers, improved acrylonitrile polymer compositions obtainable therewith, and method of preparation



United States Patent GRAFT COPGLYMERS 0F MIXTURES 0F ACRYL- AMIDES AND SULFONIC ACID COMPOUNDS 0N N-VINYL-3-MORPHOL1NONE POLYMERS, HVIPROVED ACRYLONITRILE POLYMER COM- POSITIGNS OBTAINABLE 'IHEREWITH, AND METHOD OF PREPARATION Stanley A. Murdock, Concord, Califi, Clyde W. Davis, Williamsburg, V3., and Forrest A. Ehlers, Walnut Creek, Calif, assignors to The Dow Chemical Company, Midland, Mich, a corporation of Delaware Filed Oct. 22, 1959, Ser. No. 847,972. 19 (Zlaims. (Cl. 260-455) The present invention resides in the general field of organic chemistry and contributes specifically to the polymer art, especially with respect to certain crosslinked, water-insoluble graft copolymer compositions and fiber-forming polymer blends obtainable therewith. The invention is, in this way, pertinent to the man-made synthetic textile fiber industry.

The present invention is particularly concerned with graft copolymers of mixtures of certain monomeric bisacrylamides in admixture with certain monomeric organic sulfonic acid compounds that are graft copolymerized upon preformed substrate N-vinyl-3-rnorpholinone polymers (hereinafter referred to as VM polymers). Such graft copolymeric products have especial utility as dyereceptive antistatic and stabilizing additaments for acrylonitrile polymer compositions which, advantageously, may be of the fiber-forming variety. The invention is also concerned with the compositions that may be obtained by blending the graft copolymers with acrylonitrile polymers, as well as with shaped articles which have been fabricated therefrom, that have significantly enhanced properties and characteristics as regards improvements in and relating to enhance dye-receptivity, minimizing inherent propensity to accumulate electrostatic charges and an augmented natural stability to var ious deteriorating influences, including stability against becoming deleteriously influenced and degraded upon exposure to heat at elevated temperatures and light. Within the scope and purview of the invention there is comprehended both the novel and utile graft copolymer and blended polymer compositions of the indicated varieties (as well as various shaped articles fabricated therefrom and comprised thereof) and advantageous methods for their preparation.

It is the main purpose and primary design of the present invention to provide and make available graft copolymers of certain bisacrylamide monomers admixed with certain monomeric organic sulfonic acid compounds upon preformed VM polymer substrates, which graft copolymers are especially well suited for being in corporated in acrylonitrile polymer compositions, particularly polyacrylonitrile, to serve in the indicated treble capacity of dye-assisting adjuvants, antistatic agents and stabilizing ingredients.

It is also a principal aim and concern of the invention to furnish acrylonitrile polymer compositions of the above-indicated and hereinafter more fully delineated type and shape articles therefrom that have, as intrinsic and distinguishing characteristics, excellent receptivity of and acceptability for any of a wide variety of dyestuffs; permanently imbued antistatic properties that are unusually good for and not commonly encountered in polymeric materials of the synthetic, essentially hydrophobic varieties of such substances; and efiicacious natural stability to heat and light as well as to certain chemical conditions such as alkaline environments.

The blended polymer compositions of the present invention which fulfill such ends and ofifer corollary advantages and benefits, as will hereinafter be manifest, are, in

essence, comprised of an intimate and practically inseparable blend or alloy constitution of (A) an acrylonitn'le polymer that contains in the polymer molecule at least about Weight percent of polymerized acrylonitrile (any balance being copolymerized units of at least one other ethylenically unsaturated monomeric material that is copolymerizable with acrylonitrile), which acry-lom'trile polymer preferably is of the fiber-forming variety and, most advantageously, is polyacrylonitrile and (B) a minor proportion of the beneficial graft copolymeric additament, also a subject of the invention, that functions and serves simultaneously in the treble capacity of a dye-. assisting adjuvant, permanent antistatic agent and stabilizer and which is comprised of the graft copolymerized polymerization product of (a) a mixture of monomers consisting of (1) a monomeric alkylene or alkylidene bisacrylamide or bismethacrylamide, as hereinafter more fully delineated and (2) a monomeric organic sulfonic acid compound (including free acid compounds and ester or salt derivatives) that contains a substituent, reactive vinyl group in its molecule; with (b), as a preformed polymer substrate, a VM polymer, particularly poly-N-vinyl-3-morpholinone (PVM) The method of the invention by which such compositions may be made involves incorporating the minor proportions of the polymeric additament in and with the acrylonitrile polymer base by any of several beneficial techniques, hereinafter more thoroughly defined, adapted to suitably accomplish the desired result. copsolymers themselves are made by graft copolymerizing the mixture of monomers upon the VM polymer substrate, as hereinatfer demonstrated.

Without being limited to or by the specific embodimen-ts and modes of operation set forth, the invention is exemplified in and by the following docent illustrations wherein, unless otherwise indicated, all parts and percentages are to be taken on a weight basis.

ILLUSTRATION A A polymeric additament satisfactory for use in practice of the present invention is prepared .by charging into a suitable reaction vessel about 5.25 grams of ethylene sulfonic acid; 7.5 grams of N,N-methylenebisacrylamide: 50 grams of PVM having a relative viscosity in water at 25 C. of about 1.85 at a concentration of 1 gram of the watersoluble polymer in ml. of solution; 0.13 gram of ammonium persulfate; and 200 ml. of water. charge is mixed together and its pH adjusted to about 8 with sodium hydroxide. The charge is then polymerized under an atmosphere of nitrogen at a temperature of about 50 0., with continued agitation, for a period of 1 about 16 hours. The monomers are practically completely polymerized with the PVM to make a graft copolymer product which contains about 8 percent of polymerized ethylene sulfonic acid; about 11 percent of polymerized N,N-methylenebis-acrylamide; and about 81 percent of PVM. The graft copolymerized polymeric additament is obtained from the reaction mass as a slightly colored dispersion of extremely fine particles of the graft copolymer.

Polyacrylonitrile fibers containing about 5.4 percent of the above polymeric product are prepared by impregnating filamentary structures that are in aquagel condition after having been salt-spun and wet-stretched in and with an aqueous dispersion of the graft copolymer that contains about 2 percent graft copolymer solids.

The polyacrylonitrile aquagel fiber that isemployed is obtained by extruding a spinning solution of fiber-form- I'he graft.

The-

agulating bath that contains about 42 percent of dissolved zinc chloride to form a multiple filament tow. After being spun, the tow bundle of coagulated polyacrylonitrile aquagel fiber is washed substantially free from salt upon being withdrawn from the coagulating bath and then wetstretched for orientation to a total stretched length that is about thirteen times its original extruded lengh. The aqu'agel fiber, which contains about two parts of water for each part of polymer therein, is then passed through the mentioned aqueous impregnating bath of the dispersed graft polymeric additive so as to become impregnated therewith to the indicated extent.

Following the impregnation, the .aquagel fiber is irreversible dried at 150 C. to destroy the water-hydrated structure and convert it to a finished fiber form. It is then heat set for five minutes at 150 C. The finally obtained 3 denier fiber product has a tenacity of about 3.5 grams per denier, an elongation of about 33 percent and a wet yield strength of about 0.98 gram per denier. The graft-copolymer-containing acrylonitrile polymer j fiber product is found to have excellent natural stability to heat and light as well as against becoming degraded under the influence of aqueous alkaline media at pH levels as high as 10. It is found to be nearly free of propensity to accumulate charges of static electricity upon handling; being about commensurate with viscous rayon fibers in this regard. As is widely appreciated, viscose rayon yarn and fibers are not considered to be afflicted to a troublesome degree with problems due to static.

The graft-copolymer-impregnated fiber product dyes Well to deep and level shades of coloration with Calcodur Pink ZBL, a direct type of dyestuff (Colour Index Direct Red 75, formerly Colour Index 353) and Sevron Brilliant Red 46, a basic dye formerly known as Basic Red 40 (Colour Index Basic Red 14).

The dyeing with Calcodur Pink ZBL is performed at the 4 percent level according to conventional procedure in which the fiber sample is maintained for about one hour at the boil in the dyebath which contains the dyestufi in an amount equal to about 4 percent of the weight of the fiber (OWF). The dyebath also contains sodium sulfate in an amount equal to about 15 weight percent OWF and has a bath-to-fiber weight ratio of about 30:1. After being dyed, the fiber is rinsed in water and dried for about 20 minutes at 80 C.

The dye-receptivity of the Calcodur Pink ZBL-dyed fiber is then evaluated spectrophotomethically by measuring the amount of monochromatic light having a wave length of about 520 millimicrons from a standard source that is reflected from the dyed sample. A numerical value on an arbitrarily designated scale from zero to one hundred is thereby obtained. This value represents the relative comparison of the amount of light that is reflected from a standard white tile reflector that has a reflectance value of 316 by extrapolation from the -100 scale. Lower reflectance values are an indication of better dye-receptivity in the fiber. For example, a reflectance value of about 20 or 25 to 50 or so for acrylonitrile polymer fibers dyed with 4 percent Oalcodur Pink ZBL is generally considered by those skilled in the art to be representative of a degree of dye-receptivity that readily meets or exceeds the most rigorous practical requirements and is ordinarily assured of receiving general commercial acceptance and ap-' proval. The CalcodurPink ZBL-dyed polyacrylonitrile fibers containing the above-described graft copolymeric additament in accordance with the invention has a refiectance value of about 20. In contrast, ordinary unmodh fied polyacrylonitrile fibers of the same type generally have a reflectance value of about 130 on the same numerical scale. v

The antistatic properties of the graft-copolymer-containing fiber are then determined by measuring the electrical conductance of the fiber product at various humidities. As will be appreciated by those who are skilled in the art, the

basis for such a test is that all fibers have a tendency to aosarve 2 generate static electricity upon being handled. Only those that are possessed of suflicient electrical conductance to dissipate the charge as quickly as it forms are not hampered by the bothersome effects of static electricity. Thus, a measure of the electrical conductance of a fiber is a good indication of its ability to dissipate static electricity. The conductivities of the various fiber samples tested are found by determining their electrical resistances. Resistance, of course, is the reciprocal quantity of conductivity. In order to permit various fiber samples to be compared on the common basis, the conductivities of the samples tested are actually measured as volume resistivities according to the following formula:

Volume resistivity (Resistance) (cross-sectional area) The units of volume resistivity are ohm-cmF/cm.

Prior to being tested, the copolymer-containing polyacrylonitrile fiber prepared in the indicated manner is scoured for /2 hour at the boil using about 1.0 percent on the weight of the fiber of an alkylphenoxypolyoxyethylene ethanol, non-ionic detergent, and a 30:1 volume: fiber ratio of Water. After being scoured, the fiber sample is washed thoroughly with water and dried. The actual resistivity of each sample is determined after the sample being tested is conditioned for seventy-two hours at the particular temperature and relative humidity conditions involved by tautly connecting a web-like sample of the yarn between two electrodes, each of which are 9 centimeters long spaced parallel 13 centimeters apart, and across which there is applied a 900 volt direct current potential. For purposes of comparison, the volume resistivity of cotton, wool and an unmodified polyacrylonitrile fiber (obtained in the same way as the graft-copolymer-containing fiber but without having the copolymeric additament incorporated therein) are also tested in the indicated manner along with the graft-copolymer-containing fiber in accordance with the present invention.

The results are set forth in the following tabulation which indicates the volume resistivities obtained at various relative humidities (RH) at 23 C. of each of the samples tested.

Table I VOLUME RESISTIVITIES OF VARIOUS FIBER SAMPLES COh/IPARED TO POLYACBYLONITRILE FIBERS IMPREG- NATED WITH GRAFT COPOLYMERS OF STYRENE SUL- ggNg$OID AND N,N-METHYLENEBISAGRYLAMIDE As is apparent from the foregoing, the graft-copolymercontaining fiber sample, even after being severely scoured, has electrical conductance properties much superior to ordinary polyacrylonitrile fibers and only slightly poorer than cotton. At the same time, the physical properties of the graft-copolymer-containing fiber are excellent, being about equal to those of unmodified polyacrylonitrile fibers.

' Equivalent results are obtained when the foregoing procedure is repeated excepting to impregnate the aquagel fiber with the copolymer additive prior to the stretchdrawing operation on the fiber.

ILLUSTRATION B Following the general procedure of Illustration A, about 10.0 grams of the sodium salt of 2-sulfoethylacrylate; about 7.6 grams of N,N'-methylenebisacrylamide; about 70.6 grams of PVM having a Fikentscher K-value of about 45; about 0.2 gram of ammonium persulfate and about 225 ml. of water are mixed together and the pH of the resulting mixture adjusted to a value of about 3 with HCl. The charge is polymerized for about 18 hours at 50 C. under a nitrogen atmosphere with continued agitation throughout the entire period of polymerization. Practically all of the monomers are converted to a waterinsoluble graft copolymer product which is obtained in the form of an aqueous, gel-like dispersion. The graft copolymer product contains about 11 percent of the polymerized sodium 2-sulfoethylacrylate monomer; about 8.5 percent of the polymerized N,N'-methylenebisacryl amide monomer; and about 80.5 percent of the PVM. The gelled dispersion, after being put through a Waring Blendor, is applied to a polyacrylonitrile aquagel fiber by a method in accordance with that set forth in the first illustration using about a 2.5 percent aqueous dispersion of the graft copolymer as an impregnating bath. The impregnated fiber is found to contain about 6.5 percent of the graft-copolymer product. The impregnated fiber product is readily dyeable, has low static properties and excellent stability to heat, light and alkaline media at pH levels as high as 10. When the graft-copolymer-containing fiber product is subjected to ultraviolet light exposure in an Atlas Fadeometer under standard test conditions, no perceptible break in color is observed until after 240 hours of exposure. In comparison, a plain polyacrylonitrile control sample breaks after only about 120 hours under the same conditions.

ILLUSTRATION C The procedure of Illustration B is essentially duplicated excepting to employ a graft copolymeric polymer additament which is a graft copolymer of styrene sulfonic acid and N,N'-methylenebisacrylamide on PVM prepared from the following polymerization mass which is polymerized under the same conditions and in the same Way as that of the preceding illustration:

Styrene sulfonic acid, sodium salt grams 10.05 N,N'-methylenebisacrylamide do 8.42 PVM (Fikentscher K-value 45) do 73.9 Ammonium persulfate do 0.2 Water ml 250 Polyacrylonitrile aquagel fibers are impregnated in the same way as set forth in the preceding illustrations from a 2 percent aqueous dispersion of the graft copolymer product so as to contain, upon being dried and converted to finished fiber form, about 5.3 percent OWF of the impregnated graft copolymer. The graft copolymer-containing fiber product is readily dyeable and has excellent heat and light stability. Even after being severely scoured, the graft copolymer-containing fiber sample has electrical conductance properties much superior to ordinary polyacrylonitrile fibers and only slightly poorer than cotton. At the same time, the physical properties of the graft copolymer-containing fibers are excellent, being about equal to those of the unmodified polyacrylonitrile fiber.

ILLUSTRATION D About 1.54 grams of N,N'-methylenebisacrylamide; 1.65 grams of allyl taurine; 7.45 grams of PVM having a Fikentscher K-value of about 50; 44.11 grams of Water and 0.03 gram of ammonium persulfate are mixed together. The pH of the resulting mixture is about 6. As it is commonly used, the nomenclature taurine is commonly employed to designate Z-amino-ethanesulfonic acid. The so-prepared polymerization mass is heated under a nitrogen atmosphere with continued agitation for a period of about 16 hours at a temperature of about 50 C., during which time conversion of the monomers to graft copolymer product is substantially complete. A soft, white, water-insoluble, graft-copolymer gel product is thereby ob tained which contains about 14 percent of the polymerized N,N'-methylenebisacrylamide; about 15 percent of the allyl taurine; and about 71 percent of PVM. The gelled product is readily dispersed in the aqueous medium to form a uniform dispersion of the graft copolymer by means of a Waring Blendor. When the graft copolymeric polymer additament is impregnated from a 5 percent aqueous dispersion into polyacrylonitrile aquagel fibers according to the procedure described in the foregoing, so as to obtain a fiber product with an impregnated graft-cm polymer content of about 11.3 percent, a readily dyeable fiber product is obtained. This filamentary product, when dyed with 4 percent Calcodur Pink ZBL, is found to have a reflectance value of about 20. The antistatic character istics of the graft copolymer-containing fiber product are about commensurate with those of cotton. The resulting fiber product also has excellent heat, light and alkaline stability and good physical properties comparable to those of unmodified polyacrylonitrile fibers of the same type.

ILLUSTRATION E The procedure of Example D is essentially repeated excepting to employ the following charge as the polymerized mass:

The charge polymerizes to a white, insoluble gel with a substantially complete conversion of the monomeric ingredients to graft copolymer product. The gel product is dispersed into a uniform aqueous dispersion by a Warring Blendor. Polyaorylonitrile fibers are prepared to contain about 15 percent of the polymeric additament using the general procedure set forth in Example A with a 5 percent aqueous dispersion of the graft copolymer product as the impregnating bath for the aquagel fibers. The resulting graft copolymer-containing fiber product has. good physical properties, excellent heat, light and'alkaline stability and dyes well to deep and level shades with Calcodur Pink 2BL, Calcocid Alizarine Violet, Amacel Sea/rlet BS and Sevron Brilliant Red 4G. The copolymer-containing fiber product has a reflectance value of about 18 when dyed at the 4 percent level with Calcodur Pink 2BL. The fiber product shows less static susceptibility than viscose rayon yarn.

Results similar to those set forth in the foregoing can also be obtained when other graft copolymers within the scope of the invention are employed and when the polymeric additaments are incorporated in polyacrylonitrile and other acrylonitrile copolymer fibers of the well known varieties that contain in the polymer molecule at least about weight percent of polymerized acrylonitrile to provide articles in accordance with the present invention by blending the polymeric additament and the fiber-forming acrylonitrile polymer in a spinning composition or dope prior to its extrusion and to filamentary products by either wet-spinning or dry-spinning techniques. In such instances, incidently, it may be desirable in order to secure optimum benefit in the practice of the invention to employ relatively larger quantities of the copolymeric additament than when surface impregnation was performed so that the presence of effective quantities of the additament at or near the surface of the article is assured.

Excellent results may also be achieved when other preformed VM polymer substrates are substituted for or mixed with the PVM in the prepanation of the polymeric additaments, such as copolymers of VM with N-vinyl-Z- wherein R is hydrogenor a methyl group and is selected from the group of bivalent radicals consisting of methylene, ethylene, orthoand para-phenylene, and 1,1- alkyiidene radicals that contain from 2 to about 5 carbon atoms; and (2) alkenyl group-containing organic sulfonic acids and derivatives thereof that are selected from the group of such compounds consisting of those represented by the formulae (including mixtures thereof) CH2=G (OHDp a Rm X (Aromatic organic sulfonic acid compounds) CH =CH-.-(CH SO X (III) (Alkenyl organic sulfonic acid compounds) CHFCC O O (0 H2) nSOlX (IV) (Sulfoalkylacrylate organic sulfonlc acid compounds) CH =(iO ONH- (0 Hz) n-SO X Z 1 (Aeryloyl taurine homolog compounds) and CHz=OCHz-NH(CH2)r-$O3X t (Allyl taurine homolo'g compounds) all wherein 'X is hydrogen, and alphatic hydrocmbon radical containing from 1 to 4 carbon atoms or an alkali metal ion; Y is hydrogen, chlorine or bromine; R is methyl or ethyl; Z is hydrogen or methyl; in has a numerical value in whole number increments from 0 to 2; n has a numerical value of 1 or 2; p is 0 or 1, and r is an integer with a numerical value from 1 to 4; on (b) preformed substrate VM polymers.

The N-vinyl-B-morpholinone polymers that are utilized as preformed substrates in the preparation of the graft copolymeric additaments of the present invention have, as an essential constituent of their polymeric structure, characterizing proportions of the recurring group I 1120 CH:

a -GEL As has been indicated, copolyruers of N-vinyl-3-morpholinone may also be employed. Thus, copolymers of N-vinyl-S-morpholinone with various homologous alkyl ring-substituted N-vinyl-3-morpholinone monomers may be utilized, such as copolymers of N-vinyl-3-morpholinone with N-vinyl-S-methyl-3-morpholinone, N- vinyl-5-ethyl-3-morpholinone, and the like. Copolymers of N-vinyl-3-morpholinonc with various N-vinyl lactam' polymers, suchas N-vinyl-2-pyrrolidone, li-vinyl-piperidone, N-vinyl caprolactam, N-vinyl-S-methyl-Z-pyrroli- 8 done and the like may also be prepared. Advantages are also achieved with copolymers of Nvinyl-3-morpholinone and various of the N-vinyl-Z-oxazolidinone monomers, such as NWinyl-Z-oxazolidinone, N-vinyLS- methyl-Z-oxazoiidinone, N-vinyl-5-ethyl-2-oxazolidinonc, and so forth.

These N-vinyl-morpholinone poiymers and their preparation are discussed in U.S. Patents 2,952,668, fiied April 16, 1958; 2,946,772, filed February 27, 1958; and 2,948,70-8,filed April 3, 1958; and in the co-pending ap plication for US. Patent having Serial No. 692,587, now U.S. 2,987,509, filed October 28, 1957, and entitled N- Vinyl-3-Morpholinone Compounds. Advantageously, the N-vinyl-3-morpholinone polymer that is used in the manufacture of the graft copolymer product has a Fikentscher K-value between about 10 and and, more advantageously, between about 20-30 and 60.

Beneficially, as mentioned, the N-vinyl-B-morpholinone polymer that is utilized is a water-soluble material. In cases where N-vinyl-3-morpholinone copolymers are employed that tend to water-insolubility with decreasing proportions of N-vinyl-3-morpholinone in the copolymer molecule (as is the case with copolymers of N-vinyl-3- morpholinone and N-vinyl-5-methyl-2-oxazolidinone), it is generally most desirable for the copolymer to contain at least about 40 weight percent of the N-vinyl-B-morpholinone polymerized therein. This avoids working with a product that may have a cloud (or precipitation) point in water or other aqueous solution beneath the boil.

The acrylamide monomers that are employed in the practice of the invention may be obtained by distinctly different methods, depending upon their particular chemical constitution. Thus, alkylidene bisacrylamides may be prepared from aldehydes and acrylonitrile according to the following illustrative equation:

2CHFCHCN+R'CHO (CHFCHCONH) CHR' whereas alkylene bisacrylarnides are ordinarily obtainable from' diamines and acrylic acid according to the following illustrative reaction:

wherein R is a 1 to 4 carbon atom alkyl radical, and R may be selected from the group of bivalent radicals consisting of methylene, ethylene, and ortho and para phenylene. Of course, bismethacrylamide monomers may be manufactured in analogous ways.

Typical of the various bisacrylamide and bismethacrylamide monomers that may be satisfactorily employed for the preparation of'the graft copolymeric a'dditaments of the invention are the following grouped according to the type of bivalent linkage in their structures).

Besides those specifically illustrated, other organic sulfonic acids may also be utilized for the preparation of the water-insoluble polymeric additaments of the present invention, such by way of illustration, as those which are set forth in the disclosure of United States Letters latent No. 2,527,300. In addition to the sulfonic acid monomers specifically described in the foregoing examples, others that may advantageousiy be employed in the practice of the present invention include such organic sulfouic acids as 2-propene sulfonic acid; sodium paravinylbenzene sulfonates; 2- md/ or 3-sulfopropyl acrylate; sulfoacrylic acid; sodium vinyl toluene sulfonate; potassium ortho-chloro-styrene sulfonate; 2-hydroxy-3-sulfopropyl acrylate, sodium salt; sodium 3-allyloxy-2-hydroxypropane sulfonate; 4-sulfophenyl acrylate, sodium salt; N-allyl imino di-(Z-ethane sulfonic acid); and the like. Still others are listed in the appendix following the present specification.

The graft copolymeric additaments that are employed in the practice of the invention may generally be prepared by conventional methods of polymerization, including those which have been demonstrated in the foregoing illustrative examples. In addition to the usual catalysts, including persulfates, organic and inorganic peroxides and azo type catalysts, the graft-copolymers may oftentimes be polymerized under the influence of high energy radia tion such as by means of X-rays and the like, or simply by heating and evaporating the monomer-containing polymerization mixture. The graft-copolymers may be prepared in both aqueous and organic solvent vehicles, using temperatures for the desired polymerization that may vary from about room temperature to the boiling point of the polymerization mixture. It is ordinarily satisfactory to conduct the reaction at a temperature of about 50 to 80 or 100 C. Usually, depending upon the specific factors that may be involved, the copolymerization may be accomplished satisfactorily within a time period of about 10 to 60 hours.

The compositions of the graft copolymerized polymeric additament can vary within rather wide limits. Advantageously, the content of the preformed VM polymer substrate upon which the monomeric constituents are graft copolymerized is between about 10 and about 90 percent, more advantageously between about 20 and about 80 percent, of the weight of the graft copolymerized product with the content of either monomeric constituent being between about 10 and about 90, more advantageously, from about 30 to about 7 mole percent of the polymerized monomer substituents in the graft copolymerized product. It may frequently be desirable for the monomeric constituents that are polymerized to be employed in nearly equivalent or about commensurate or equal molar proportions in the preparation of the graft copolymeric additament and for the quantity of the preformed VM polymer substrate to be at least half of the constitution of the graft copolymer product.

The polymerization system that is employ-ed for the preparation of the graft copolymers employed in the present invention may consist of as much as 50 percent by weight of the monomers and preformed VM polymer substrate to be graft-copolymerized in the aqueous medi um. The amount of monomeric materialthat is provided in the copolymerization system may be influenced some what by the manner in which it is intended to incorporate the product in the synthetic polymer compositions in order to provide the compositions of the invention.

If, for example, it is intended to incorporate the graft copolymer products by blending them into a fiber-forming composition prior to its fabrication into shaped articles, the copolymerization system may, if desired contain about equal proportions by weight of the charged graft copolymerizable materials and the polymerization medium which, preferably, is miscible with and tolerable in the spinning solution solvent being used. In such cases, the graft copolymer product may ordinarily be obtained as an easily dispersed gel that, after being dried and isolated from unreacted monomer, may readily be directly incorporated in the fiber-forming composition.

If the incorporation of the graft copolymeric additament in a fiber-forming composition is to be achieved by impregenation therewith of an already-formed shaped article of the composition; it may be desirable to efiect the polymerization so as to directly form the graft copolymerization system as a suitable applicating emulsion or suspension of the graft copolymeric product. For such purposes, the polymerization system may be prepared to contain as little as 2-10 percent by weight of the graftcopolymerizing ingredients. Preferably, such a graft copolymerization may be conducted under the influence of vigorous agitation to facilitate preparation of an emulsified or thoroughly dispersed product. It may also be beneficial under such circumstances to incorporate a dispersant or emulsifying agent in the polymerization system to facilitate obtaining a stable and homogeneous emulsified product. Such a method for preparing the graft copolymeric additaments that are employed in the present invention may be especially appropriate when they are intended to be applied to acrylonitrile polymer fibers and the like that are derived from aquagels in the course of their manufacture, such as the acrylonitrile polymer fibers that are wet spun from aqueous saline solutions of the fiber-forming polymer.

In many instances, as has been demonstrated, the emulsified, water-insoluble, graft copolymeric additaments may be impregnated into the fiber while it is in a swollen or gel condition, as an acrylonitrile polymer fiber in an aquagel condition, in order to obtain the desired graftcopolymer-containing product.

In this connection, when it is desired to blend the graft copolymeric additament in a synthetic polymer fiberforming solution prior to its extrusion, such as an aqueous saline acrylonitrile polymer solution, the water-insoluble copolymer may be physically reduced by comminution to a sufiiciently fine state to permit its dispersion in spinnable condition throughout the blended spinning solution in the event that it is otherwise insoluble in the solvent. While this may be accomplished by diverse techniques, it is generally advantageous to comminute the polymeric additament in the presence of the non-dissolving solvent, such as an aqueous saline polyacrylonitrile solvent, to form a stable suspension that may be more conveniently blended with the spinning solution of the synthetic polymer, such as an aqueous saline acrylonitrile polymer spinning solution. Thus, if the aqueous, saline polyacrylonitrile solvent that is being employed in an aqueous solution of zine chloride or its equivalent that contains at least about 55 percent and preferably about 60 percent by weight of dissolved zinc chloride, it may be advantageous to comminute the graft copolymeric additament while it is in a mixture with the saline solvent solution that contains between about 5 and 10 percent by weight of the copolymer. Analogous procedures may be employed when other solvents are involved. Ball or rod mills or other attrition apparatus may be employed beneficially for the comminution. It is generally beneficial under such circumstances to avoid the use of balls or rods that are made of metal since they may contaminate the product, especially when aqueous saline solvents are utilized. Porcelain or other ceramic parts may usually be employed with advantage. A stable suspension of the graft co: polymeric additament in the acrylonitrile polymer solvent that is suitable for blending in the spinning solution of the acrylonitrile polymer to provide a spinnable compo- ;sition may usualy be obtained by milling the mixture of polymeric additament and solvent for an extended period that may exceed hours. The suspension that is thereby obtained may then be directly blended in the proper proportions with the acrylonitrile polymer spinning solution to provide a composition in accordance with the present invention.

I If desired, the graft-copolymer-containing acrylonitrile polymer compositions may comprise as much as 20 or more weight percent of the graft copolymeric additament, based on the weight of the composition. Usually, howsesame ever, suitable properties and characteristics and better fiber-forming properties in a given composition may be achieved when lesser proportions of the polymeric additament are incorporated therein. An appreciable improvement in dye-receptivity, anti-static properties and stability may frequently be obtained when a quantity of the graft copolymeric additament is less than 0.5 weight percent is employed. Advantageously, an amount between about 2 and weight percent of the polymeric additaments may thus be utilized in the composition. Greater advantages may often accrue when the amount of the polymeric additament that is incorporated in the composition is not in excess of about 10 weight percent, based on the weight of the composition.

As has been indicated, the graft copolymeric additaments may be incorporated in the acrylonitrile polymer compositions according to various techniques. Thus, for example, the polymeric additament and the acrylonitrile polymer may be directly blended in order to provide the composition which, incidentally, may be used for any desired fabrication purpose in addition'to fiber-forming and the like. Beneficially, the polymers may be comminuted, either separately or in combination, before being intimately blended together by mechanical or other means. The blended polymers may be prepared into suitable fiber-forming systems by dispersing them in a suitable liquid medium. Or, the compositions may be provided in fiber-forming system by sequentially dispersing the polymers in any desired order in a suitable medium, as by incorporating the graft-copolymeric additament in a prepared acrylonitrile polymer spinning solution, dope or the like. As is obvious, the polymeric additaments employed in the practice of the present invention are ordinarily insoluble, despite the fact that they are readily dispersib-le in most solvents.

As is evident from the exemplifying illustrations heretofore included, a highly advantageous technique for providing the compositions, particularly when acrylonitrile polymer fiber products are involved, is to apply or impregnate the graft copolymeric additament in a known manner from an aqueous dispersion thereof to a shaped acrylonitrile polymer article that is in an aquagel condition. Thus, an acrylonitrile polymer filamentary article that has been spun from an aqueous saline spinning solution may be conveniently passed, after its coagulation and while it is in an aquagel condition, through a water bath containing a dispersed graft copolymeric additament in order to impregnate the filament with the graft-copolymer and provide a composition and an article in accordance with the invention. In addition, in situ polymerization techniques may be employed to provide the graft copolymeric additament in the fiber product. Thus, the compositions may be made by impregnating an acrylonitrile polymer, such as a shaped article in aquagel or other swollen condition, with the unpolymerized monomers and the preformed VM polymer substrate and graft copolymerizing them therein by means of radiation, dry heat or steam with or without other catalyzing influence.

The compositions of the invention may advantageously be utilized in or with fiber-forming systems of any desired type in order to provide fibers and the like according to procedures and techniques that are conventionally employed for such purposes in the preparation of fibers and such related shaped articles as filaments, strands, yarns, tows, threads, cords and other funicular structures, ribbons, tapes, films, foils, sheets and the like which may be manufactured from synthetic polymeric materials. It is frequently desirable to employ concentrated solutions of salts or mixtures of salts as the dispersing or dissolving media for such purposes. Such solutions may, as has been indicated, contain at least about 55 weight percent, based on the weight of the solution, of zinc chloride or other knownsaline solvents for the polymer. Acrylonitrile polymer fiber products that are spun from saline fiber-forming systems ma by way of further illustration, be coagulated in more dilute saline solutions of a like or similar nature and may then be processed after coagulation according to conventional techniques of washing, -stretching, drying, finishing and the like with the modification of the present invention being accomplished prior or subsequent to the spinning as may be desired and suitable in particular instances.

The acrylonitrile polymer fiber products in accordance with the present invention (one of which is schematically illustrated in the sole FIGURE of the accompanying drawing) have excellent physical properties and other desirable characteristics for a textile material and have a high capacity for and are readily and satisfactorily dyeable to deep and level'shades with any of a wide variety of dyestuffs. For example, they may be easily and successfully dyed according to conventional procedures using acid, vat, acetate, direct, naphtho-l and sulfur dyes.

Such dyestufis, by way of didactic illustration, as Calcocoid Alizarine Violet (Colour Index 61710, formerly Colour Index 1080), Sulfanthrene Red 313 (Colour Index Violet 2), Amacel Scarlet GB (Colour Index Direct Red 1also known as Amacel Scarlet BS, and having American Prototype Number 244), Calcodur Pink 2BL (Colour Index 353, also more recently, Colour Index Direct Red '75), Naphthol AS'MX (Colour Index 35527), Fast Red TRN Salt (Colour Index Azoic Diazo Component 11), and Immedial Bordeaux G (Colour Index Sulfur Brown 12.) may advantageously be employed for such purposes.

Other dyestuffs, by way of further illustration, that may be utilized beneficially on the graft copolymer-con- .taining, polymer blended fiber products of the invention include such direct cotton dyes as Chlorantine Fast Green SBLL (Colour Index Direct Green 27), Chlorantine Fast Red 7B (Colour Index Direct Red 81) Pontamine Green GX Conc. 125 percent (Colour Index Direct Green 6), Calcomine Black EXN Conc. (Colour Index Direct Black 38), Niagara Blue NR (Colour Index Direct Blue 151) and Eric Fast Scarlet 4BA (Colour Index Direct Red 24); such acid dyes an Anthraquinone Green GN (Colour Index Acid Green 25), Sulfonine Brown 2R (Colour Index Acid Orange 51), Sulfonine Yellow 2G (Colour Index Acid Yellow 40), Xylene Milling Black 213 (Colour Index Acid Black 26A), Xylene Milling Blue FF (Colour Index Acid Blue 61), Xylene Fast Rubine 3GP =PAT (Colour Index Acid Red 57), Calcocid Navy Blue R Cone. (Colour Index Acid Blue Calcocid Fast Blue BL (Colour Index Fast Blue 59), Calcocid Milling Red 3R (Colour Index Acid Red 151), Alizarine Levelling Blue 2R (Colour Index Acid Blue 51), Amacid Azo Yellow G Extra (Colour Index Acid Yellow 63); such mordant-acid dyes as Alizarine Light Green GS (Colour Index Acid Green 25); such basic dyes as Brilliant Green Crystals (Colour Index Basic Green 1) and Rhodamine B Extra S (Colour Index Vat Blue 35); such vat dyestuffs as Midland Vat Blue R Powder (Colour Index Vat Blue 35), Sulfanthrene Brown G Paste (Colour Index Vat Brown 5), Sulfanthrene Blue 2B Dbl. paste :(Colour Index Vat Blue 5), and Sulfanthrene Red 3B paste (Colour Index Vat Violet 2); various soluble vat dyestufis; such acetate dyes as Celliton Fast Brown 3RA Extra CF (Colour Index Disperse Orange 5), Celliton Fast Rubine BA CF (Colour Index Dispersed Red 13), Artisil Direct Red 3B? and Celanthrene Red 3BN Conc. (Both Colour Index Dispersed Red 15), Celanthrene Pure Blue BRS 400 percent (Colour Index Dispersed Bluel) and Acctamine Yellow N (Colour Index Dispersed Yellow 32); B-naphthol -2- chloro-4-nitroaniline, an azoic dye; such sulfur dyes as Katigen Brilliant Blue GGS High Conc. (Colour Index Sulf. Blue 9) and Indo Carbon CLGS (Colour Index Sulf. Blue 6); and various premetalized dyestuffs.

The dyed products are generally lightfast. and stable to heat and are well imbued with a resistance to crocking. In addition, the dyed products exhibit good Wash- APPENDIX Representative of the various monomeric organic sulfonic acid compounds that may be employed satisfactorily in the practice of the present invention are those set forth in the following listing, wherein they are grouped according to the several designated types. The list, by no means exhaustive, includes species not mentioned in the foregoing.

Aromatic alkenyl-containing sulfonic acid compounds (Formula II):

Para-styrene sulfonic acid Ortho-styrene sulfonic acid Para-isopropenyl benzene sulfonic acid Para-viny benzyl sulfonic acid Ortho-isopropenyl benzyl sulfonic acid Sodium para-styrene sulfonate Potassium ortho-styrene sulfonate Methyl para-styrene sulfonate Ethyl para-vinyl benzyl sulfonate Ortho vinyl benzene sulfonic acid Isopropyl ortho-isopropenyl benzene sulfonate n-Butyl ortho-styrene sulfonate Tertiary butyl para-styrene sulfonate 2-chloro-4-vinyl benzene sulfonic acid 4-bromo-2-isopropenyl benzene sulfonic acid 3-vinyl toluene-6-sulfonic acid, sodium salt 2-ethyl-4-vinyl-benzene sulfonic acid 2,3-dichloro-4-vinyl benzene sulfonic acid 2,3,5-tribromo-4-vinyl benzene sulfonic acid 2-chloro-3-vinyl-toluene-6-sulfonic acid 2,3-diethy1-4-vinyl-benzyl sulfonate, sodium salt Alkenyl sulfonic acid compounds (Formula III):

Ethylene sulfonic acid Sodium ethylene sulfonate Potassium ethylene sulfonate Methyl ethylene sulfonate Isopropyl ethylene sulfonate l-propene 3-sulfonic acid l-propene l-sulfonic acid, sodium salt l-propene 2-sulfonic acid, ethyl ester l-butylene 4-sulfonic acid, n-butyl ester l-butylene 3-sulfonic acid Tertiary butylene sulfonic acid Sulfoalkylacrylate compounds (Formula IV):

Sulfomethylacrylate 2-sulfoethylacrylate Sulfomethylmethacrylate, sodium salt 2-sulfoethylmethacrylate, methyl ester 2-sulfoethylmethacrylate, potassium salt Acryloyl taurine and homolog compounds (Formula V) N-acryloyl taurine N-acryloyl taurine, sodium salt N-methacryloyl taurine, methyl ester 7 N-methacryloyl taurine, potassium salt N-acryloyl taurine, ethyl ester N-acryloyl-aminomethane sulfonic acid N-methacryloyl-aminomethane sulfonic acid, sodium salt Methyl N-methacryloyl-aminomethane sulfonate Allyl taurine and homolog compounds (Formula VI):

Allyl taun'ne Allyl taurine, sodium salt Allyl taurine, potassium salt Methallyl taurine Methallyl taurine, methyl ester Methallyl tanrine, isopropyl ester N-allyl-aminomethane sulfonic acid Sodium N-allyl-aminomethane sulfonate Lithium N-methallyl-aminomethane sulfonate n-Butyl N-allyl-aminomethane sulfonate What is claimed is:

1. Composition comprising between about and 99.5 weight percent, based on composition weight, of (A) a polymerized ethylenically unsaturated monomeric material containing ,at least about 80 weight percent of polymerized acrylonitrile, and (B) between about 20 and about 0.5 weight percent, based on composition weight, of a graft copolymer of (a) from about 10 to about weight percent, based on graft copolymer weight, of a mixture of monomers consisting of (1) from about 10 to about 90 mole percent of an acrylamide monomer of the formula:v

(CHg=(il-CONR)2G (I) wherein R is selected from the group consisting of hydrogen and methyl and G is selected from the group of bivalent radicals consisting of methylene, ethylene, orthophenylene, para-phenylene, and 1,-l-alkylidene radicals containing from 2 to about 5 carbon atoms; and (2) from about 90 to 10 mole percent of an alkenyl group-containing organic sulfonic acid compound selected from the group consisting of those represented by the formulae:

onz=o cm) s 0 3X CH2=OH- (CH2) m s 02X (III) CH2=CC o 0 (CH2) rr-SO3X z (IV) om=oo ONE-(CH2) s 0 3X cm: oo HzNH- (CH2) n-s 03X wherein X is selected from the group consisting of hydrogen, aliphatic hydrocarbon radicals containing from 1 to 4 carbon atoms and alkali metals; Y is selected from the group consisting of hydrogen, chlorine and bromine; R is selected froim the group consisting of methyl and ethyl; Z is selected from the group consisting of hydrogen and methyl; m is an integer from 0 to 2; n is an integer from 1 to 2; p is an integer from O to 1; and r is an integer from 1 to 4; and (b) from about 90 to about 10 weight percent, based on graft copolymer weight of a polymerized monoethylenically unsaturated monomeric material containing at least about 10 weight percent of polymerized N-vinyl-3-morpholinone and up to about 90 weight percent of another polymerized N-vinyl-heterocyclic compound which compound is copolymerizable with N-vinyl- B-morpholinone.

2. The composition of claim 1, wherein the content of said graft copolymer is at least about 50 weight percent of said N-vinyl-B-morpholinone polymer, based on graft copolymer weight.

3. The composition of claim 1, wherein said graft copolymer is comprised of between about 20 and 80 weight percent of said N-vinyl-3-morpholinone polymer with the balance of the weight of said graft copolymer being comprised of about equal molar proportions of each of said acrylamide monomer and said sulfonic acid compound graft copolymerized on said N-vinyl-3-morpholinone polymer.

4. The composition of claim 1, wherein the graft copolymer is N,N-methylenebisacrylamide and ethylene 'sulfonic acid on poly-N-vinyl-3-morpholin0ne.

5. The composition of claim 1, wherein the graft copolymer is N,N-methylenebisacrylamide and sodium sulfonate on poly-N-vinyl-3-rnorpholinone.

6. The composition of claim 1, wherein the graft copolymer is N,N'-methylenebisacrylamide and the sodium salt of acryloyl taurine on poly-N-vinyl-3 morpholinone.

7. The composition of claim 1, wherein the graft copolymer is N,N '-methylenebisacrylamide andthe sodium salt of 2-sulfoethylacrylate on poly-N-vinyl-3-1'norpholinone.

8. The composition of claim 1, wherein the graft copolymer is N,N-methylenebisacrylamide and the sodium salt of allyl taurine on poly-N-vinyl-3-morpholinone.

9. The composition of claim 1, wherein the acrylonitrile polymer is polyacrylo-nitrile.

, V 10. The composition of claim 1 dispersed in a solvent for polyacrylonitrile. v

11. A filamentary shaped article comprised of the composition of claim 1.

12. Method for the preparation of a dye-receptive, anti-,

static, stable to light and heat, synthetic, hydrophobic polymer composition which comprises immersing an.

(CHpCii-CONRMG (I) wherein R is selected from the group consisting of hydro gen and methyl and G is selected from the group of bi: valent radicals consisting of methylene, ethylene, orthophenylene, paraphenylenc, and, 1,1-alkylidene radicals containing from 2 to about carbon atoms; and (2) from. about 90 to about mole percent of an alkenyl groupcontaining organic sulfonic acid compound selected from the group consisting of those of the formulae:

om=o (CHrl'r-SOaX CHz=0H(OHz) SO3X (n1) om=o-o o O-(OHzls-SOQX i av) capo-o ONE-(0H2) Peon;

is V (v) CH2=CCH2NH(CHz)nSO3X V r I) wherein X is seelcted from the group consisting of hydrogen, aliphatic hydrocarbon radicals containing from 1 to 4 carbon atoms and alkali metals; Y is selected from the group consisting of hydrogen, chlorine and bromine; R is selected from the group consisting of methyl and ethyl; Z is selected from the group consisting of hydrogen and methyl; m is an integer from 0 to 2; n is an integer from 1 to 2; p is an integer from 0 to 1; and r is an integer from 1 to 4; and (b) between about 90 and about 10 weight percent, based on graft copolymer weight, of a polymerized monoethylenically unsaturated monomeric material containing at least about 10 weight percent of polymerized N-vinyl-3-morpholinone and up to about 90 weight percent of another polymerized N-yinyl-heterocyclic compound wliich compound is copolymerizable with N-vinyl- 3-morpholinone, until between about0.5 and about percent of said graft copolymer, based on resulting dry composition weight, is incorporated in said aquagel; and drying said graft copolymer-containing aquagel to convert it from the aquagel condition to a finished shaped article form. 1

13. The method of claim 12, wherein said acrylonitrile p yme s p y rylonim'le.

14. The method of claim 12, wherein said N-vinyb morpholinone polymer is po1y-N-vinyl-3-rnorpholinone.

15. Graft copolymer of between about 10 and about 90 weight percent of (a) a mixture of monomers consisting of (1) from about 10 to about 90 mole percent of an arcrylamide monomer of the formula:

wherein R is selected from the group consisting of hydro gen and methyl and G is selected from the group of hivalent radicals consisting of methylene, ethylene, orthophenylene, para-phenylene, and 1,1-alkylidene radicals containing from 2 to about 5 carbon atoms; and (2) fromabout 90 to about 10 mole percent of an alkenyl groupcontaining organic sulfonic acid compound selected from the group consisting of those represented by the formulae:

wherein X is selected from the group consisting of hydrogen, aliphatic hydrocarbon radicals containing -from 1 to 4 carbon atoms and alkali metals; Y is selected from the group consisting of hydrogen, chlorine and bromine; R is selected from the group consisting of methyl and ethyl; Z is selected from the group consisting of hydrogen and methyl; m is an integer-from 0 to 2; n is an integer from 1 to 2; p is an integerfrom 0 to l; and r is an integer from 1 to 4; and (b) from about 90 to about 10 weight percent of a polymerized monoethylenically unsaturated monomeric material containing at least about 10 weight percent of polymerized N-vinyl-3-morpholinone and up to about 90 weight percent of another polymerized N-vinylheterocyclic compound which compound is copolymerizable with N-vinyl-3-morpholinone.

16. The graft copolymer of claim 15, containing from about 20. to about percent of about equal molar proportions of said mixture of monomers graft copolymerized upon from about 80 to about 20 percent of said N- vinyl-3-morpholinone polymer. 7

17. The graft copolymer of claim 15, wherein said mixture of monomers consists of (1) from about 30 to about 70 mole percent of said acrylamide monomer of said Formula I and (2) from about 70 to about 30 mole percent of said organic sulfonic acid compound selected from the group consisting of those represented by said Formulae II, III, IV, V and VI.

18. The graft copolymer of claim 15, wherein said N- vinyl-S-morpholinone polymer is poly-N-vinyl-3-morpholinone.

19. Method for the preparation of a graft copolymer, which comprises polymerizing between about 10 and about weight percent, based on resulting graft copolymer weight, of a mixture of monomers consisting of (1) from about 10 to about 90 mole percent of an acrylamide monomer of the formula:

R oHi=('J--ooNR)1G wherein R is selected from the group consisting of hydrogen and methyl and G isselected from the group of hivalent radicals consisting of methylene, ethylene, ortho- CHpCf-G Hz-NH(CH2) r-S 03X Z (VI) wherein X is selected from the group consisting of hydrogen, aliphatic hydrocarbon radicals containing from 1 to 4 carbon atoms and alkali metals; Y is selected from the group consisting of hydrogen, chlorine and bromine; R is selected from the group consisting of methyl and ethyl; Z is selected from the group consisting of hydrogen and methyl; m is an integer from 0 to 2; n is an integer from 1 to 2; p is an integer from 0 to 1; and r is an integer from 1 to 4; with (b) between about 90 and about 10 Weight percent of a polymerized monoethylenically unsaturated monomeric material containing at least about 10' weight percent of polymerized N-vinyl-3-morpholinone and up to about 90 weight percent of another polymerized N-vinyl-heterocyclic compound Which compound is copolymerizable with N-vinyl-3-morpholinone.

References Cited in the file of this patent UNITED STATES PATENTS 

1. COMPOSITION COMPRISING BETWEEN ABOUT 80 AND 99.5 WEIGHT PERCENT, BASED ON COMPOSITION WEIGHT, OF (A) A POLYMERIZED ETHYLENICALLY UNSATURATED MONOMERIC MATERIAL CONTAINING AT LEAST ABOUT 80 WEIGHT PERCENT OF POLYMERIZED ARCYLONITRILE, AND (B) BETWEEN ABOUT 20 AND ABOUT 0.5 WEIGHT PERCENT, BASED ON COMPOSITION WEIGHT, OF A GRAFT COPOLYMER OF (A) FROM ABOUT 10 TO ABOUT 90 WEIGHT PERCENT, BASED ON GRAFT COPOLYMER WEIGHT, OF A MIXTURE OF MONOMERS CONSISTING OF (1) FROM ABOUT 10 TO ABOUT 90 MOLE PERCENT OF AN ACRYLAMIDE MONOMER OF THE FORMULA: 